阅读说明：本技术 包含嵌段共聚物的粒料和由该粒料得到的成型体 (Pellet containing block copolymer and molded body obtained from the pellet ) 是由 川原萌 赤井真 中田加那予 小野友裕 于 2019-10-04 设计创作，主要内容包括：提供充分防胶着的、含有具有包含丙烯酸甲酯单元的聚合物链段的丙烯酸类嵌段共聚物的粒料,由该粒料生产率良好地提供不有损该丙烯酸类嵌段共聚物所具有的优异特性的成型体。一种粒料,其包含：丙烯酸类嵌段共聚物(I),其具有包含甲基丙烯酸酯单元的至少1个聚合物链段(A1)、和包含丙烯酸酯单元的至少1个聚合物链段(B1)；和,丙烯酸类聚合物(II),其含有甲基丙烯酸甲酯单元35质量％以上、且230℃、载荷3.8kg的条件下的熔体流动速率(MFR)为10g/10分钟以上,丙烯酸类嵌段共聚物(I)的聚合物链段(B1)中所含的丙烯酸酯单元仅由丙烯酸甲酯单元和通式CH-2＝CH-COOR～1(1)(式中,R～1表示碳数4～12的有机基团)所示的丙烯酸酯(1)单元构成,丙烯酸类嵌段共聚物(I)和丙烯酸类聚合物(II)的质量比(I)/(II)为90/10～40/60。(A pellet containing an acrylic block copolymer having a polymer segment comprising a methyl acrylate unit, which is sufficiently anti-blocking, is provided, and a molded article having excellent characteristics of the acrylic block copolymer is provided from the pellet with good productivity. A pellet, comprising: an acrylic block copolymer (I) having at least 1 polymer segment (a1) containing methacrylate ester units, and at least 1 polymer segment (B1) containing acrylate ester units; and an acrylic polymer (II) containing a methyl methacrylate unit 35 by mass% or more, and a Melt Flow Rate (MFR) of 10g/10 min or more under a condition of 230 ℃ and a load of 3.8kg, wherein the acrylate units contained in the polymer segment (B1) of the acrylic block copolymer (I) are composed of only methyl acrylate units and the general formula CH 2 ＝CH‑COOR 1 (1) (in the formula, R 1 An organic group having 4 to 12 carbon atoms), and the mass ratio (I)/(II) of the acrylic block copolymer (I) to the acrylic polymer (II) is 90/10 to 40/60.)

1. A pellet, comprising:

an acrylic block copolymer (I) having at least 1 polymer segment (a1) containing methacrylate ester units, and at least 1 polymer segment (B1) containing acrylate ester units; and the combination of (a) and (b),

an acrylic polymer (II) containing 35% by mass or more of a methyl methacrylate unit and having a Melt Flow Rate (MFR) of 10g/10 min or more under a load of 3.8kg at 230 ℃,

the acrylate ester unit contained in the polymer segment (B1) of the acrylic block copolymer (I) is composed of only methyl acrylate unit and the general formula CH₂＝CH-COOR¹(1) The acrylate (1) unit shown in the formula, wherein R is¹Represents an organic group having 4 to 12 carbon atoms,

the mass ratio (I)/(II) of the acrylic block copolymer (I) to the acrylic polymer (II) is 90/10-40/60.

2. The pellet of claim 1, comprising 200 to 2000ppm of an anti-sticking agent.

3. A molded article obtained by molding the pellet according to claim 1 or 2.

Technical Field

The present invention relates to: pellets containing an acrylic block copolymer having a polymer segment comprising a methyl acrylate unit, and a molded article obtained by molding the pellets.

Background

Acrylic block copolymers having a polymer segment containing an acrylate unit and a polymer segment containing a methacrylate unit have been studied for their properties for various applications such as adhesive adhesives, soft materials, and resin modifiers. Among the above-mentioned acrylic block copolymers, an acrylic block copolymer containing a methyl acrylate unit in a polymer segment containing an acrylate unit is being studied in a laminate with, for example, a vinyl chloride resin, because of its excellent durability against a plasticizer, excellent adhesion, and the like (for example, patent document 1).

When a molded article is produced from an acrylic block copolymer by various molding methods such as injection molding and extrusion molding, the acrylic block copolymer serving as a raw material thereof is usually produced in the form of granular pellets. However, the adhesion of an acrylic block copolymer containing a methyl acrylate unit in a polymer segment containing an acrylate unit is remarkable, and even when pellets are produced from the acrylic block copolymer and left for a while, the pellets become an aggregate of the pellets, i.e., a massive large block, due to their own weight, and it is difficult to return the pellets to a state simply by applying an external force to the block. In the case where the raw material is in the form of a massive large block, the block needs to be formed again into a pellet shape by some means when a molded article is produced, which causes a serious problem in productivity and quality control of the molded article.

For the anti-blocking of the pellets, a method of adhering an anti-blocking agent such as ethylene bis stearamide to the pellet surface is considered. However, when ethylene bis stearamide is used as an anti-blocking agent, there are problems such as a decrease in transparency of the resulting molded article and occurrence of build-up.

In addition, as another measure for preventing blocking, a method of adding a lubricant to an acrylic block copolymer has been studied (for example, patent document 2).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2016/175119

Patent document 2: japanese patent laid-open publication No. 2003-253005

Disclosure of Invention

Problems to be solved by the invention

In the anti-blocking method described in patent document 2, the pellets may not be sufficiently anti-blocked. Therefore, the addition of the anti-blocking agent was attempted by increasing the amount of the anti-blocking agent to an extremely large extent, but in a molded article produced from the pellet, the excellent properties (for example, transparency) of the acrylic block copolymer tend to be impaired. An object of the present invention is to provide: pellets of an acrylic block copolymer having a polymer segment comprising a methyl acrylate unit, which are sufficiently anti-blocking, are excellent in productivity and provide a molded article which does not impair the excellent properties of the acrylic block copolymer.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object, and as a result, have found that: when a specific acrylic block copolymer having a polymer segment comprising a methyl acrylate unit and another specific acrylic polymer different therefrom are compounded at a specific mass ratio and produced in the form of pellets, the blocking can be sufficiently prevented. Further, it was found that: from the pellets, a molded article can be produced without impairing the excellent properties of the acrylic block copolymer.

According to the present invention, the above object is achieved by providing:

[1] a pellet, comprising:

an acrylic block copolymer (I) having at least 1 polymer segment (a1) containing methacrylate ester units, and at least 1 polymer segment (B1) containing acrylate ester units; and the combination of (a) and (b),

an acrylic polymer (II) containing 35% by mass or more of a methyl methacrylate unit and having a Melt Flow Rate (MFR) of 10g/10 min or more under a load of 3.8kg at 230 ℃,

the acrylate ester unit contained in the polymer segment (B1) of the acrylic block copolymer (I) is composed of only methyl acrylate unit and the general formula CH₂＝CH-COOR¹(1) (in the formula, R¹An organic group having 4 to 12 carbon atoms) and an acrylic ester (1),

the mass ratio (I)/(II) of the acrylic block copolymer (I) to the acrylic polymer (II) is 90/10-40/60;

[2] the pellet according to [1], which comprises 200 to 2000ppm of an anti-blocking agent;

[3] a molded article obtained by molding the pellet according to [1] or [2 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, pellets containing an acrylic block copolymer having a polymer segment comprising a methyl acrylate unit, which are sufficiently anti-blocking, can be obtained, and from the pellets, a molded article can be obtained with good productivity without impairing the excellent properties of the acrylic block copolymer.

Detailed Description

The present invention will be described in detail below. In the present specification, "(meth) acrylate" is a generic term for "methacrylate" and "acrylate", and "(meth) acrylic acid" is a generic term for "methacrylic acid" and "acrylic acid".

< acrylic Block copolymer (I) >)

The acrylic block copolymer (I) contained in the pellets of the present invention has at least 1 polymer segment (a1) containing methacrylate ester units, and at least 1 polymer segment (B1) containing acrylate ester units, the acrylate ester units contained in the polymer segment (B1) consisting of only methyl acrylate units and a general formula CH₂＝CH-COOR¹(1) (in the formula, R¹An organic group having 4 to 12 carbon atoms) is used.

Examples of the methacrylic acid ester which becomes the structural unit of the polymer segment (a1) include: alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and isobornyl methacrylate;

methacrylates having no functional group other than alkyl methacrylates such as phenyl methacrylate and benzyl methacrylate;

functional group-containing methacrylates such as alkoxyalkyl methacrylates (e.g., methoxyethyl methacrylate and ethoxyethyl methacrylate), diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate; and the like.

Among them, alkyl methacrylate is preferable, methyl methacrylate, ethyl methacrylate, and propyl methacrylate are more preferable, and methyl methacrylate is further preferable from the viewpoint of economical availability and excellent durability and weather resistance of the obtained polymer segment (a 1).

The methacrylate ester unit of the polymer segment (a1) may be obtained from only 1 type of methacrylate ester, or may be obtained from 2 or more types of methacrylate ester. The ratio of the methacrylate ester unit contained in the polymer segment (a1) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polymer segment (a 1). The polymer segment (a1) may be composed of 100% by mass of methacrylate ester units, that is, may be composed of only methacrylate ester units.

The polymer segment (a1) may contain other monomer units within a range not detrimental to the effects of the present invention. Examples of the other monomer include acrylic acid esters; vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic anhydride, and fumaric acid; vinyl monomers having functional groups such as (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl chloride, and vinylidene chloride; aromatic vinyl monomers such as styrene, α -methylstyrene, p-methylstyrene and m-methylstyrene; conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene, propylene, isobutylene, and octene; lactone monomers such as epsilon-caprolactone and valerolactone. The amount of the monomer unit composed of these other monomers is usually small relative to the total monomer units of the polymer segment (a1), and the ratio of the other monomer units contained in the polymer segment (a1) is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

The glass transition temperature (Tg) of the polymer segment (A1) is preferably 50 to 150 ℃, more preferably 60 to 140 ℃, and still more preferably 70 to 130 ℃. When the glass transition temperature of the polymer segment (A1) is within the above range, the tackiness at a high temperature (for example, 50 ℃) tends to decrease (the tackiness resistance tends to improve) when stored as pellets.

The acrylic block copolymer (I) may contain 2 or more polymer segments (a1), but in the above case, the methacrylate ester unit and other monomers constituting these polymer segments (a1) are optionally the same or different.

The weight average molecular weight of the polymer segment (a1) is not particularly limited, but is preferably in the range of 1000 to 50000, more preferably 4000 to 20000. When the weight average molecular weight of the polymer segment (a1) is less than 1000, the resultant acrylic block copolymer (I) may have insufficient aggregating power. When the weight average molecular weight of the polymer segment (a1) is more than 50000, the melt viscosity of the obtained acrylic block copolymer (I) may be high, and the productivity of the acrylic block copolymer (I) and the moldability of pellets containing the obtained acrylic block copolymer (I) may be poor. In the present specification, the weight average molecular weight (Mw) is a weight average molecular weight in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method.

The polymer segment (B1) contains an acrylate unit, and the acrylate unit contained in the polymer segment (B1) is composed of only a methyl acrylate unit and a general formula CH₂＝CH-COOR¹(1) (in the formula, R¹An organic group having 4 to 12 carbon atoms) is used.

Examples of the acrylic ester (1) include acrylic esters having no functional group such as alkyl acrylates having an alkyl group having 4 to 12 carbon atoms, e.g., n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, etc.; and acrylates having a functional group such as 2-ethoxyethyl acrylate, 2- (diethylamino) ethyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenoxyethyl acrylate.

Among these acrylates (1), from the viewpoint that the phase separation of the polymer segment (a1) and the polymer segment (B1) becomes clearer, acrylates having no functional group are preferable, alkyl acrylates having an alkyl group having 4 to 12 carbon atoms are more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are further preferable. N-butyl acrylate is more preferable because a molded article which is soft, has high adhesion, and has excellent durability tends to be easily obtained from the pellet.

The acrylate (1) unit contained in the polymer segment (B1) may be obtained from only 1 type of acrylate (1), or may be obtained from 2 or more types of acrylate (1).

The mass ratio of methyl acrylate units to acrylate (1) units in the polymer segment (B1), methyl acrylate/acrylate (1), is preferably 90/10 to 10/90. When the mass ratio is within the above range, the acrylic block copolymer (I) is excellent in the balance between the resistance to a plasticizer due to methyl acrylate units and the flexibility due to acrylate (1) units. The mass ratio and the methyl acrylate/acrylic ester (1) are preferably 90/10 to 25/75, more preferably 85/15 to 37/63, and further preferably 80/20 to 42/58, from the viewpoint of more excellent resistance to a plasticizer and balance between flexibility. The mass ratio of the methyl acrylate unit to the acrylic ester (1) unit may be determined by¹H-NMR was measured.

The upper limit of the ratio of the methyl acrylate unit in the acrylate ester unit of the polymer segment (B1) is preferably 90%, more preferably 85%, and still more preferably 80%. The lower limit of the ratio of the methyl acrylate unit in the polymer segment (B1) is preferably 25%, more preferably 37%, and still more preferably 42%.

The ratio of the acrylate ester units composed only of the methyl acrylate units and the acrylate ester (1) units contained in the polymer segment (B1) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polymer segment (B1). The polymer segment (B1) may be composed of 100% by mass of acrylate units, that is, may be composed of only acrylate units.

The polymer segment (B1) may contain other monomer units than acrylate units within a range not to impair the effects of the present invention. Examples of the other monomers constituting the above-mentioned unit include methacrylic acid esters; vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic anhydride, and fumaric acid; vinyl monomers having functional groups such as (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl chloride, and vinylidene chloride; aromatic vinyl monomers such as styrene, α -methylstyrene, p-methylstyrene and m-methylstyrene; conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene, propylene, isobutylene, and octene; lactone monomers such as epsilon-caprolactone and valerolactone. The amount of the monomer unit composed of these other monomers is usually small relative to the total monomer units of the polymer segment (B1), and the ratio of the other monomer units contained in the polymer segment (B1) is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

In addition, the acrylic block copolymer (I) may contain 2 or more polymer segments (B1), but in the above case, the combination of the acrylate units constituting these polymer segments (B1) is optionally the same or different.

The polymer segment (B1) may be composed of a random copolymer of methyl acrylate and acrylic acid ester (1) constituting the polymer segment (B1), a block copolymer, a graft copolymer, or a tapered block copolymer (gradient copolymer). When the acrylic block copolymer (I) contains 2 or more polymer segments (B1), the structures of the polymer segments (B1) may be the same or different.

The glass transition temperature (Tg) of the polymer segment (B1) is more preferably-45 to 55 ℃, still more preferably-35 to 50 ℃, still more preferably-30 to 45 ℃, and still more preferably-30 to 25 ℃. When the glass transition temperature is in this range, a molded article obtained from the pellets tends to be easily soft, have high adhesion, and have excellent durability.

The difference in glass transition temperature between the polymer segment (A1) and the polymer segment (B1) in the acrylic block copolymer (I) is preferably 50 ℃ or more, more preferably 70 ℃ or more.

In the acrylic block copolymer (I), the polymer segment (A1) is referred to as "A1"; when the polymer segment (B1) is referred to as "B1", it is preferably represented by the following general formula:

(A1-B1)_n

(A1-B1)_n-A1

A1-(A1-B1)_n

(A1-B1)_n-Z

(B1-A1)_n-Z

(wherein n represents an integer of 1 to 30, and Z represents a coupling site (a coupling site formed by a reaction of a coupling agent with a polymer terminal to form a chemical bond)). The value of n is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 4. )

Of these structures, a structure in which a polymer segment (a1) is bonded to each of both ends of a polymer segment (B1) is preferable.

Specifically, it is preferably represented by the following general formula:

(A1-B1)_m

(A1-B1)_n-A1

B1-(A1-B1)_m

(A1-B1)_m-Z

(B1-A1)_m-Z

(wherein n represents an integer of 1 to 30, m represents an integer of 2 to 30, and Z represents a coupling site (a coupling site formed by a reaction of a coupling agent with a polymer terminal to form a chemical bond)). The value of m is preferably 2 to 15, more preferably 2 to 8, and further preferably 2 to 4. The value of n is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 4. )

Of the above structures, more preferred is (A1-B1)_n、(A1-B1)_n-A1、A1-(A1-B1)_nThe linear block copolymer is more preferably a diblock copolymer represented by A1-B1 and a triblock copolymer represented by A1-B1-A1, and particularly preferably a triblock copolymer represented by A1-B1-A1. These can be used alone in1 kind, also can be combined with more than 2 kinds and use.

The content of the polymer segment (a1) in the acrylic block copolymer (I) is preferably 5 to 40% by mass.

When the content of the polymer segment (A1) is less than 5% by mass, the acrylic block copolymer (I) tends to have high fluidity and be easily in a liquid state, and when pellets are produced from the acrylic block copolymer (I) and the acrylic polymer (II) described later, the pellets tend to be unable to maintain their shapes even when cut with, for example, an underwater cutter or the like. When the content of the polymer segment (A1) exceeds 40 mass%, flexibility tends to be impaired.

The content of the polymer segment (a1) in the acrylic block copolymer (I) is preferably 8 to 35% by mass, more preferably 14 to 31% by mass, from the viewpoint of obtaining pellets having excellent flexibility.

The weight average molecular weight of the acrylic block copolymer (I) is preferably 30000 to 250000, more preferably 40000 to 200000, further preferably 50000 to 180000, and further preferably 60000 to 160000, from the viewpoint of compatibility with the acrylic polymer (II) described later and processability of the resulting pellets. When the weight average molecular weight of the acrylic block copolymer (I) is less than 30000, the aggregating force of the acrylic block copolymer (I) becomes insufficient, and the durability and the like of the obtained molded article may be poor. In addition, there may be a case where a defect such as bleeding due to the acrylic block copolymer (I) occurs on the surface of the obtained molded article. On the other hand, if the weight average molecular weight of the acrylic block copolymer (I) exceeds 250000, the melt viscosity may become excessively high, and the productivity and processability may be poor. Further, the compatibility with the acrylic polymer (II) described later is low, and there are cases where the transparency of the obtained pellets and the molded article obtained from the pellets is insufficient, or the physical properties of the obtained pellets and the molded article obtained from the pellets are uneven.

The molecular weight distribution (Mw/Mn) of the acrylic block copolymer (I) is preferably 1.0 to 1.5. When the molecular weight distribution of the acrylic block copolymer (I) is in the above range, the aggregating force of the acrylic block copolymer (I) tends to be improved, and the mold contamination during molding of the obtained pellets tends to be suppressed. From the above viewpoint, the molecular weight distribution is more preferably 1.0 to 1.4, and still more preferably 1.0 to 1.3. In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) refer to a number average molecular weight and a weight average molecular weight in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method.

< acrylic Polymer (II) >)

The acrylic polymer (II) contained in the pellet of the present invention is a polymer different from the acrylic block copolymer (I), and contains 35 mass% or more of a methyl methacrylate unit, and has a Melt Flow Rate (MFR) of 10g/10 min or more under a load of 3.8kg at 230 ℃. By combining the acrylic polymer (II) and the acrylic block copolymer (I) satisfying both the content of the methyl methacrylate unit and the MFR, a sufficiently anti-blocking pellet can be produced. In addition, the molded article produced from the obtained pellets does not impair the excellent properties of the acrylic block copolymer (I).

The content of the methyl methacrylate unit contained in the acrylic polymer (II) is preferably 37% by mass or more. By using such an acrylic polymer (II), a sufficiently anti-blocking pellet can be produced more reliably.

From the viewpoint of compatibility with the acrylic block copolymer (I) and processability of the resulting pellets, the MFR of the acrylic polymer (II) under the conditions of a temperature of 230 ℃ and a load of 3.8kg is preferably 10 to 400g/10 min. When the MFR is less than 10g/10 min, the melt viscosity is high, and therefore, the anti-blocking property tends to be hardly exhibited. When the MFR exceeds 400g/10 min, the melt viscosity is low, and hence the kneading property during processing tends to be insufficient.

The acrylic polymer (II) is roughly classified into an acrylic block copolymer (II-1) having a polymer segment containing a methyl methacrylate unit, a random copolymer containing a methyl methacrylate unit, or a methyl methacrylate homopolymer (II-2).

< acrylic Block copolymer (II-1) >)

The acrylic block copolymer (II-1) which can be contained in the pellet of the present invention is an acrylic block copolymer having a polymer segment containing a methyl methacrylate unit and having a content of the methyl methacrylate unit in the copolymer of 35% by mass or more.

Among the above-mentioned acrylic block copolymers (II-1), from the viewpoint of more excellent compatibility with the acrylic block copolymer (I) and more excellent flexibility, the acrylic block copolymer (II-1A) is preferably an acrylic block copolymer (II-1A) having at least 1 polymer segment (A2) containing a methyl methacrylate unit and at least 1 polymer segment (B2) containing an acrylate unit, and the acrylate unit contained in the polymer segment (B2) is composed of only the general formula CH₂＝CH-COOR²(2) (in the formula, R²An organic group having 4 to 12 carbon atoms) is used as a monomer.

The ratio of the methyl methacrylate unit contained in the polymer segment (a2) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polymer segment (a 2). The polymer segment (a2) may be composed of 100% by mass of methyl methacrylate units, that is, may be composed of only methyl methacrylate units.

The polymer segment (a2) may contain other monomer units than methyl methacrylate within a range not to impair the effects of the present invention. Specific examples of the other monomers include: methacrylic acid esters and acrylic acid esters other than methyl methacrylate; vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic anhydride, and fumaric acid; vinyl monomers having functional groups such as (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl chloride, and vinylidene chloride; aromatic vinyl monomers such as styrene, α -methylstyrene, p-methylstyrene and m-methylstyrene; conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene, propylene, isobutylene, and octene; lactone monomers such as epsilon-caprolactone and valerolactone. The amount of the monomer unit composed of these other monomers is usually small relative to the total monomer units of the polymer segment (a2), and the ratio of the other monomer units contained in the polymer segment (a2) is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

The glass transition temperature (Tg) of the polymer segment (A2) is preferably 50 to 150 ℃, more preferably 70 to 140 ℃, and still more preferably 80 to 130 ℃. When the glass transition temperature of the polymer segment (A2) is within the above range, the tackiness at a high temperature (for example, 50 ℃) tends to decrease (the tackiness resistance tends to improve) when stored as pellets.

The acrylic block copolymer (II-1A) may contain 2 or more polymer segments (A2), but in the above case, the methyl methacrylate units and other monomers constituting these polymer segments (A2) are optionally the same or different.

The weight average molecular weight of the polymer segment (a2) is not particularly limited, but is preferably in the range of 1000 to 50000, more preferably 4000 to 20000. When the weight average molecular weight of the polymer segment (A2) is less than 1000, the resultant acrylic block copolymer (II-1A) may have insufficient aggregating power. When the weight average molecular weight of the polymer segment (A2) is more than 50000, the melt viscosity of the resulting acrylic block copolymer (II-1A) may be high, and the productivity of the acrylic block copolymer (II-1A) and the moldability of pellets containing the resulting acrylic block copolymer (II-1A) may be poor.

The polymer segment (B2) contains an acrylate unit, and the acrylate unit contained in the polymer segment (B2) is represented by the general formula CH₂＝CH-COOR²(2) (in the formula, R²An organic group having 4 to 12 carbon atoms) is used as a monomer.

Specific examples of the acrylic ester (2) are the same as the 1 type of acrylic ester (1) which is a structural unit of the polymer segment (B1) of the acrylic block copolymer (I).

Among these acrylates (2), from the viewpoint that the phase separation of the polymer segment (a2) and the polymer segment (B2) becomes clearer, acrylates having no functional group are preferable, alkyl acrylates having an alkyl group having 4 to 12 carbon atoms are more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are further preferable. N-butyl acrylate is more preferable because a molded article which is soft, has high adhesion, and has excellent durability tends to be easily obtained from the pellet.

The acrylate (2) unit constituting the acrylate unit contained in the polymer segment (B2) may be obtained from only 1 type of acrylate (2), or may be obtained from 2 or more types of acrylate (2).

The ratio of the acrylate unit contained in the polymer segment (B2) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the polymer segment (B2). The polymer segment (B2) may be composed of 100% by mass of acrylate units, that is, may be composed of only acrylate units.

The polymer segment (B2) may contain other monomer units than acrylate units within a range not to impair the effects of the present invention. Specific examples of the other monomers are the same as those of other monomers which can be a structural unit of the polymer segment (B1) of the acrylic block copolymer (I). The amount of the monomer unit composed of these other monomers is usually small relative to the total monomer units of the polymer segment (B2), and the ratio of the other monomer units contained in the polymer segment (B2) is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

The glass transition temperature of the polymer segment (B2) is preferably-100 to 40 ℃, more preferably-80 to 35 ℃, and still more preferably-70 to 30 ℃. When the glass transition temperature of the polymer segment (B2) is within the above range, flexibility is excellent also in a low-temperature region. Among the alkyl acrylates, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate are preferable because the glass transition temperature of the polymer segment (B2) falls within the above-mentioned suitable range and they are easily available.

In addition, the acrylic block copolymer (II-1A) may contain 2 or more polymer segments (B2), but in the above case, the combination of the acrylate units constituting these polymer segments (B2) may be the same or different.

The difference in glass transition temperature between the polymer segment (A2) and the polymer segment (B2) in the acrylic block copolymer (II-1A) is preferably 70 ℃ or higher, more preferably 100 ℃ or higher.

For the above acrylic block copolymer (II-1A), the polymer segment (A2) is referred to as "A2"; when the polymer segment (B2) is referred to as "B2", it is preferably represented by the following general formula:

(A2-B2)_i

(A2-B2)_i-A2

A2-(A2-B2)_i

(A2-B2)_i-Z

(B2-A2)_i-Z

(wherein i represents an integer of 1 to 30, and Z represents a coupling site (a coupling site formed by a reaction of a coupling agent with a polymer terminal to form a chemical bond)). The value of i is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 4. )

Of these structures, a structure in which a polymer segment (a2) is bonded to each of both ends of a polymer segment (B2) is preferable.

Specifically, it is preferably represented by the following general formula:

(A2-B2)_k

(A2-B2)_i-A2

B2-(A2-B2)_k

(A2-B2)_k-Z

(B2-A2)_k-Z

(wherein i represents an integer of 1 to 30, k represents an integer of 2 to 30, and Z represents a coupling site (a coupling site formed by a reaction of a coupling agent with a polymer terminal to form a chemical bond)). The value of k is preferably 2 to 15, more preferably 2 to 8, and further preferably 2 to 4. The value of i is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 4. )

Of the above structures, more preferred is (A2-B2)_i、(A2-B2)_i-A2、A2-(A2-B2)_iThe linear block copolymer is more preferably a diblock copolymer represented by A2-B2 and a triblock copolymer represented by A2-B2-A2, and particularly preferably a triblock copolymer represented by A2-B2-A2. These can be used alone in1 kind, also can be combined with more than 2 kinds and use.

The methyl methacrylate units contained in the acrylic block copolymer (II-1A) are preferably all contained only in the polymer segment (A2), and the polymer segment (A2) is more preferably composed only of methyl methacrylate units. The content of the methyl methacrylate unit in the acrylic block copolymer (II-1A) is preferably 35 to 60% by mass. When the content of the methyl methacrylate unit is less than 35% by mass, the acrylic block copolymer (II-1A) tends to have high adhesiveness, and when the acrylic block copolymer (I) is mixed to produce pellets, the pellets may not be able to maintain their shape even when they are cut with, for example, an underwater cutter. When the content of the methyl methacrylate unit exceeds 60 mass%, flexibility tends to be impaired.

The content of the methyl methacrylate unit in the acrylic block copolymer (II-1A) is preferably 35 to 57% by mass, more preferably 37 to 54% by mass, from the viewpoint of obtaining a pellet having excellent flexibility.

The weight average molecular weight of the acrylic block copolymer (II-1A) is preferably 20000 to 250000, more preferably 30000 to 200000, further preferably 40000 to 180000, and further preferably 50000 to 160000, from the viewpoints of compatibility with the acrylic block copolymer (I) and processability of the resulting pellets. When the weight average molecular weight of the acrylic block copolymer (II-1A) is less than 30000, the aggregating force of the acrylic block copolymer (II-1A) may become insufficient, and the durability and the like of the resulting molded article may be poor. Further, there may be a case where a defect such as bleeding due to the acrylic block copolymer (II-1A) occurs on the surface of the obtained molded article. On the other hand, when the weight average molecular weight of the acrylic block copolymer (II-1A) exceeds 250000, the melt viscosity may become excessively high, resulting in poor productivity and processability. Further, the compatibility with the acrylic block copolymer (I) is low, and there are cases where the transparency of the obtained pellets and the molded article obtained from the pellets is insufficient or where there are variations in the physical properties of the obtained pellets and the molded article obtained from the pellets.

In the acrylic block copolymer (II-1A), the molecular weight distribution (Mw/Mn) is preferably 1.0 to 1.5. When the molecular weight distribution of the acrylic block copolymer (II-1A) is in the above range, the aggregating power of the acrylic block copolymer (II-1A) tends to be improved and the mold contamination during molding of the obtained pellets tends to be suppressed. From the above viewpoint, the molecular weight distribution is more preferably 1.0 to 1.4, and still more preferably 1.0 to 1.3.

The MFR of the acrylic block copolymer (II-1A) under the conditions of 230 ℃ and a load of 3.8kg is preferably 20g/10 min or more, more preferably 30g/10 min or more. When the MFR is less than the above lower limit, the miscibility with the acrylic block copolymer (I) tends to be insufficient, and the compatibility and transparency tend to be impaired. When the MFR is too high, the melt viscosity tends to be low, and hence the kneading property during processing tends to be insufficient, and therefore, it is preferably 350g/10 min or less, more preferably 300g/10 min or less. When the MFR exceeds the upper limit, melt kneading tends to be insufficiently performed.

The method for producing the acrylic block copolymers (I), (II-1) and (II-1A) is not particularly limited, and these acrylic block copolymers can be produced by a production method according to a known method. In general, as a method for obtaining a block copolymer having a narrow molecular weight distribution, a method of living-polymerizing a monomer as a structural unit can be employed. Examples of such a living polymerization method include the following: a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see, for example, Japanese patent application laid-open No. 11-335432); a method of living anion polymerization in the presence of an inorganic acid salt such as an alkali metal salt or an alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator (see, for example, Japanese examined patent publication (Kokoku) No. 7-25859); a method of living anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see, for example, Japanese patent application laid-open No. 6-93060); atom Transfer Radical Polymerization (ATRP) (see, for example, macromol. chem. phys., 2000, 201, p1108 to 1114), and the like.

Among the above-mentioned production methods, the method of living anionic polymerization in the presence of an organoaluminum compound is less inactivated during the polymerization, and therefore, the incorporation of a homopolymer is less, and the obtained block copolymer is high in transparency. Further, since the polymerization conversion of the monomer is high, the residual monomer in the block copolymer is small, and when pellets containing the acrylic block copolymer are produced, the generation of bubbles can be suppressed. Further, the molecular structure of the polymer segment containing an alkyl methacrylate unit is highly syndiotactic, and the durability of the resulting pellet containing the acrylic block copolymer is improved. Further, since living anion polymerization can be carried out under relatively mild temperature conditions, there is an advantage that environmental load (electric power applied to a refrigerator mainly for controlling polymerization temperature) can be reduced in the case of industrial production. From the above-mentioned viewpoints, the acrylic block copolymer is preferably produced by a method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound.

As the living anionic polymerization method in the presence of the above-mentioned organoaluminum compound, for example, the following methods can be employed: in the organic lithium compound and the following general formula (3)

AlR³R⁴R⁵(3)

(in the formula (3), R³、R⁴And R⁵Each independently represents an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, an aralkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an aryloxy group optionally having a substituent or an N, N-disubstituted amino group, or R³Is any of the above groups R⁴And R⁵And integrated to form an arylenedioxy group optionally having a substituent. ) In the presence of the organoaluminum compound shown above, an ether compound such as dimethyl ether, dimethoxyethane, diethoxyethane or 12-crown-4 is further added to the reaction system as required; and (meth) acrylic acid esters are polymerized with nitrogen-containing compounds such as triethylamine, N ' -tetramethylethylenediamine, N ', N "-pentamethyldiethylenetriamine, 1,4,7,10, 10-hexamethyltriethylenetetramine, pyridine, and 2,2 ' -bipyridine.

Examples of the organic lithium compound include: alkyllithium or alkyldilithium such as n-butyllithium, sec-butyllithium, and tetramethylenedilithium; aryl lithium or aryl dilithium such as phenyl lithium or xylyl lithium; lithium aralkyl or dilithium aralkyl such as benzyl lithium and dilithium generated by the reaction of diisopropenyl benzene with butyl lithium; lithium amide such as lithium diisopropylamide; lithium alkoxides such as lithium methoxide.

Further, as the organoaluminum compound represented by the above general formula (3), isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2, 6-di-t-butylphenoxy) aluminum, isobutyl [2, 2' -methylenebis (4-methyl-6-t-butylphenoxy) ] aluminum and the like are preferable from the viewpoints of high or low polymerization activity, easiness of handling and the like.

< acrylic random copolymer or methyl methacrylate homopolymer (II-2) >)

The acrylic random copolymer or methyl methacrylate homopolymer (II-2) which can be contained in the pellet of the present invention is the acrylic random copolymer (II-2A) or methyl methacrylate homopolymer (II-2B) containing 35 mass% or more of methyl methacrylate units.

The acrylic random copolymer (II-2A) preferably mainly contains methyl methacrylate units, more preferably contains 80 mass% or more, and still more preferably contains 90 mass% or more of methyl methacrylate units. The acrylic random copolymer (II-2A) having a methyl methacrylate unit content within the above range tends to have more excellent compatibility with the acrylic block copolymer (I) and to not impair the excellent properties of the acrylic block copolymer (I).

The acrylic random copolymer (II-2A) may contain a monomer unit other than methyl methacrylate. Examples of the other monomer include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, methacrylic acid esters (excluding methyl methacrylate) such as dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornene methacrylate, and isobornyl methacrylate; acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornene acrylate, isobornyl acrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid, and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene, myrcene, and the like; aromatic vinyl compounds such as styrene, α -methylstyrene, p-methylstyrene and m-methylstyrene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene fluoride, and the like.

Among these other monomers, methacrylic acid esters (excluding methyl methacrylate), acrylic acid esters, and methacrylic acid are preferable. In addition, methyl acrylate is more preferable from the viewpoint of more excellent anti-blocking performance and ease of acquisition.

The content of the other monomer unit is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less.

The methyl methacrylate homopolymer (II-2B) is a polymer comprising only methyl methacrylate units, and may comprise other monomer units. The methyl methacrylate homopolymer (II-2B) is more excellent in compatibility with the acrylic block copolymer (I), and tends not to impair the excellent characteristics of the acrylic block copolymer (I).

The stereoregularity of the acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) is not particularly limited, and isotactic, heterotactic or syndiotactic copolymers can be used.

The MFR of the acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) is preferably 10 to 400g/10 min at 230 ℃ under a load of 3.8 kg. When the MFR is less than 10g/10 min, the melt viscosity is high, and therefore, the anti-blocking property tends to be hardly exhibited. When the MFR exceeds 400g/10 min, the melt viscosity is low, and hence the kneading property during processing tends to be insufficient.

The weight average molecular weight of the acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) is preferably 50000 to 150000. The weight average molecular weight is in the above range, so that the compatibility with the acrylic block copolymer (I) is good, and the transparency is high when the copolymer is formed into pellets or molded articles. Further, the weight average molecular weight is more preferably 60000 to 130000, still more preferably 70000 to 120000, from the viewpoint of balance between compatibility with the acrylic block copolymer (I) and anti-blocking property.

The acrylic random copolymer (II-2A) may be a mixture of 2 or more copolymers having different compositions. The acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) may be a mixture of 2 or more polymers having different molecular weights or tacticity, or a mixture of polymers obtained by different production methods.

The method for producing the acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) (hereinafter, (II-2A) or (II-2B) is also referred to as the polymer (II-2)) is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, and bulk polymerization. As the initiator used in the polymerization, a radical polymerization initiator is preferable, and examples of the radical polymerization initiator include azo compounds such as Azobisisobutyronitrile (AIBN) and azobis γ -dimethylvaleronitrile; benzoyl peroxide, cumyl peroxide, neodecanoate peroxide, diisopropyl peroxydicarbonate, tert-butylcumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide and the like. The radical polymerization initiator is usually used in an amount of 0.05 to 0.5 part by mass based on 100 parts by mass of the total monomers used for producing the polymer (II-2). The polymerization is usually carried out at a temperature of 50 to 140 ℃ for usually 2 to 20 hours, and a chain transfer agent may be used for controlling the molecular weight of the polymer (II-2). Examples of the chain transfer agent include methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, ethyl thioglycolate, mercaptoethanol, thio- β -naphthol, and thiophenol. The chain transfer agent is usually used in an amount of 0.005 to 0.5% by mass based on the total monomers used for producing the polymer (II-2).

Examples of commercially available products of the acrylic random copolymer (II-2A) or the methyl methacrylate homopolymer (II-2B) include "PARAPET (registered trademark) H1000B" (MFR: 22g/10 min (230 ℃ C., 37.3N)), "PARAPET (registered trademark) GF" (MFR: 15g/10 min (230 ℃ C., 37.3N)) [ trade names, Kuraray Co., Ltd., (manufactured by Ltd.), "ACRYREX CM-211" (MFR: 16g/10 min (230 ℃ C., 37.3N)) [ manufactured by CHIMEI corporation ], and the like.

The pellet of the present invention comprises the acrylic block copolymer (I) and the acrylic polymer (II) in a mass ratio (I)/(II) of 90/10 to 40/60. The acrylic block copolymer (I) and the acrylic polymer (II) are contained in the pellets in such a mass ratio, whereby pellets sufficiently prevented from being stuck can be obtained without impairing the excellent characteristics of the acrylic block copolymer (I). The mass ratio (I)/(II) is preferably 85/15 to 50/50, more preferably 80/20 to 60/40, from the viewpoint of more excellent anti-blocking performance and more effective exertion of the excellent properties of the acrylic block copolymer (I).

The total content of the acrylic block copolymer (I) and the acrylic polymer (II) contained in the pellet of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

In the production of the pellets of the present invention, other components such as additives may be added to the acrylic block copolymer (I) and the acrylic polymer (II) within a range not to impair the characteristics of the acrylic block copolymer (I) and the acrylic polymer (II).

The pellet of the present invention can be produced by melt-extruding a mixture of the acrylic block copolymer (I), the acrylic polymer (II), and other components added as needed to form a strand, and cutting the strand with an underwater cutter, a central heating cutter, a strand cutter, or the like. The melt extrusion is usually carried out at 130 to 240 ℃.

The pellet of the present invention is not particularly limited in its form as long as it can produce a molded article described later, and generally has a substantially cylindrical or substantially spherical (ellipsoidal) form. The maximum diameter of the pellet obtained in the present invention is preferably 2 to 8mm, more preferably 2 to 6 mm. The maximum diameter of the pellets was determined from each shape as follows: the maximum cylinder height can be determined by measuring the maximum cylinder height with a commercially available length gauge, and the longest side of the ellipsoid can be determined by measuring the maximum cylinder height with a commercially available length gauge in the case of a substantially spherical shape.

The anti-blocking agent may be attached to the pellets of the present invention. As a method for adhering the anti-blocking agent to the surface of the pellet, for example, a method of directly mixing the pellet and the anti-blocking agent may be mentioned. Examples of the direct mixing device include a horizontal cylindrical mixer, a V-type mixer, a double cone type mixer, a ribbon type mixer, a cone type screw mixer, a high-speed flow type mixer, a rotary disk type mixer, an air stirring type mixer, a gravity drop type mixer, and a stirring type mixer. Further, the pellets may be put into an aqueous solution containing the anti-blocking agent to adhere the anti-blocking agent to the pellets.

As the anti-sticking agent, for example, there can be used: alflow H50T (manufactured by Nippon Aerosil Co., Ltd., ethylene bis stearamide), Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica), talc, calcium carbonate, acrylic resin fine particles, and the like. However, it is preferable to use an anti-blocking agent containing no ethylene bis-stearamide, talc or calcium carbonate so as not to impair the transparency and the like of the molded article produced from the pellet of the present invention. The amount of these antiblocking agents to be added is preferably 200 to 2000ppm, particularly preferably 300 to 1700ppm, based on the mass of the pellets, from the viewpoint of achieving both antiblocking performance and transparency.

< shaped body >

The molded article of the present invention is produced by various molding methods using the pellet as a raw material.

The raw material for the molded article of the present invention may contain, in addition to the above pellets, depending on the purpose and the like: other polymers, softening agents, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, flame retardants, foaming agents, colorants, coloring agents, fluorescent agents, refractive index control agents, fillers, curing agents, anti-sticking agents, electrical conductivity imparting agents, thermal conductivity imparting agents, electromagnetic wave shielding property imparting agents, antibacterial agents, and other additives. These components contained as required may be contained in the molded article alone in1 kind, or may be contained in 2 or more kinds.

The pellets are composed of an acrylic block copolymer and therefore have excellent weather resistance, but by adding an antioxidant, an ultraviolet absorber and a light stabilizer to the molded article of the present invention, further high weather resistance can be exhibited.

Examples of the antioxidant include a phenol-based antioxidant and a phosphorus-based antioxidant. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers. Examples of the light stabilizer include hindered amine light stabilizers.

These molded articles may contain 1 kind of the above-mentioned monomer or 2 or more kinds of the monomer. Among these, it is a preferable embodiment that the molded article contains all of the antioxidant, the ultraviolet absorber, and the light stabilizer.

The amount of each of the agents added to the molded article is preferably 0.01 to 1.0 part by mass, more preferably 0.03 to 0.60 part by mass, per 100 parts by mass of the pellet.

The lubricant is added to impart lubricity to the surface of the molded article and to improve the scratch-preventing effect. Examples of the lubricant include unsaturated fatty amides such as oleamide and erucamide; saturated fatty amides such as behenamide and stearamide, butyl stearate, stearyl alcohol, glyceryl monostearate, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, zinc stearate, hydrogenated castor oil, stearamide, oleamide, ethylene bisstearamide, silicone oil, modified silicone oil and the like. From the viewpoint of compatibility between transparency and lubricity of the molded body surface, silicone oils and modified silicone oils are preferable, and non-reactive silicone oils having side chains modified with polyethers are particularly preferable.

The lubricant may be contained in the molded article in1 kind alone, or may be contained in 2 or more kinds. The amount of the lubricant added to the molded article is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.30 part by mass, per 100 parts by mass of the pellet.

Examples of the other polymer include acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers; olefin resins such as polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; an ethylene-based ionomer; styrene resins such AS polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, and the like; styrene-methyl methacrylate copolymer; polyester resins such as polyethylene terephthalate, amorphous polyethylene terephthalate (PET-G), polybutylene terephthalate, and polylactic acid; polyamides such as nylon 6, nylon 66, and polyamide elastomers; a polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymers; a polyacetal; polyvinylidene fluoride; a polyurethane; modified polyphenylene ether; polyphenylene sulfide; a silicone rubber modified resin; an acrylic rubber; a silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin rubbers such as IR, EPR and EPDM. The other polymer may be contained in the molded article alone by 1 kind, or may be contained by 2 or more kinds.

Examples of the filler include inorganic fibers such as glass fibers and carbon fibers, and organic fibers; inorganic fillers such as calcium carbonate, talc, titanium oxide, silica, clay, barium sulfate, magnesium carbonate, magnesium hydroxide, and aluminum hydroxide; carbon black, and the like. The filler may be contained in the molded article in1 kind alone, or in 2 or more kinds.

When the inorganic fiber or the organic fiber is contained, durability can be imparted to the molded article obtained. When the inorganic filler is contained, the molded article obtained can be imparted with heat resistance and weather resistance.

Further, if titanium oxide is contained, the obtained molded article is easily provided with light-shielding properties. The amount of titanium oxide added to the molded article is preferably 20 to 250 parts by mass, more preferably 30 to 150 parts by mass, per 100 parts by mass of the pellet.

When the raw material of the molded article contains a curing agent, the molded article of the present invention can be suitably used as a curing-type molded article. Examples of the curing agent include a light curing agent such as a UV curing agent, a heat curing agent, and the like, and examples thereof include benzoins, benzoin ethers, benzophenones, anthraquinones, benzils, acetophenones, diacetyls, and the like. Specific examples thereof include benzoin, α -hydroxymethylbenzoin, α -tert-butylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α -hydroxymethylbenzoin methyl ether, α -methoxybenzoin methyl ether, benzoin phenyl ether, benzophenone, 9, 10-anthraquinone, 2-ethyl-9, 10-anthraquinone, benzil, 2-dimethoxy-1, 2-diphenylethan-1-one (2, 2-dimethoxy-2-phenylacetophenone), diacetyl and the like. The curing agent may be contained in the molded article in1 kind alone, or in 2 or more kinds.

From the viewpoint of improving the effect of the above curing agent, for example, esters such as acrylic acid, methacrylic acid, α -cyanoacrylic acid, α -haloacrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, and acrylic acid esters, methacrylic acid esters, crotonic acid esters, and maleic acid esters; (ii) acrylamide; (ii) methacrylamide; acrylamide derivatives such as N-methylolacrylamide, N-hydroxyethylacrylamide, and N, N- (dihydroxyethyl) acrylamide; methacrylamide derivatives such as N-methylolmethacrylamide, N-hydroxyethyl methacrylamide, and N, N- (dihydroxyethyl) methacrylamide; vinyl esters; a vinyl ether; mono-N-vinyl derivatives; styrene derivatives and the like; oligomers containing the above monomers as constituent components, and the like, may be further contained in the raw material of the molded article obtained in the present invention. From the viewpoint of improving durability, esters such as acrylic esters, methacrylic esters, crotonic esters, and maleic esters; a vinyl ether; a styrene derivative; and an oligomer containing the aforementioned monomer as a constituent. In addition to these monomers, a crosslinking agent comprising a monomer or oligomer having 2 or more functions may be contained.

As a raw material for the molded article of the present invention, the pellet of the present invention can be used as it is. When the pellets of the present invention further contain other components such as polymers and additives added as needed, a method of temporarily melt-mixing these raw materials is recommended in order to improve the dispersibility of each component contained in the raw materials. The melt mixing can be carried out by a known apparatus such as a kneader, an extruder, a mixing roll, a Banbury mixer, or the like. From the viewpoint of improving the kneading property and compatibility between the pellets of the present invention and components to be added as needed, a twin-screw extruder is particularly preferably used. The temperature at the time of mixing can be appropriately adjusted depending on the pellets of the present invention and the components to be added as needed, and the mixing can be usually performed at a temperature in the range of 110 ℃ to 300 ℃. As described above, when the raw material for the molded article of the present invention further contains other components such as polymers and additives, which are added as needed, in addition to the pellets of the present invention, the raw material for the molded article can be obtained in any form such as pellets and powder.

The molded article of the present invention can be obtained by molding a raw material of the molded article by a generally used molding method. Examples of the molding method include a melt molding method in which the molding is heated and melted, such as extrusion molding, injection molding, compression molding, blow molding, calender molding, and vacuum molding, and a solution casting method. Among these molding methods, a melt molding processing method is suitable from the viewpoint of handling of the pellets of the present invention and the like. By this molding method, a molded article having any shape such as a mold, a tube, a sheet, a film, a fibrous material, a laminate having a polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II), and the like can be obtained.

When the molded article of the present invention is a single-layer article, a single-layer article comprising the acrylic block copolymer (I) and the acrylic polymer (II) can be produced by extrusion molding or injection molding of the raw material of the molded article (for example, the pellet of the present invention). Examples of the extrusion molding method include a T-die method and an inflation method, and among them, the T-die method is suitable. By extrusion molding, the single-layer body can be produced without using a solvent, and can be produced by a relatively simple production apparatus. The single-layer body is produced by extrusion molding, so that the production process can be simplified and the production cost of the single-layer body can be reduced.

According to the T-die method, for example, a raw material of the molded article (for example, the pellet of the present invention) is heated and melted, and extruded from the T-die, thereby producing a single-layer body.

When the molded article of the present invention is a laminate, a laminate having a polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II) and a substrate layer can be produced by extrusion molding a raw material of the molded article (for example, the pellet of the present invention) onto the substrate layer. Examples of the extrusion molding method include a T-die method and an inflation method, and among them, the T-die method is suitable. By extrusion molding, a laminate can be produced without using a solvent, and can be produced by a relatively simple production apparatus. By producing the laminate by extrusion molding, the production process can be simplified, and the production cost of the laminate can be reduced.

According to an extrusion lamination process, which is an example of the T-die method, for example, a laminate comprising a polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II), and a base material layer can be produced by heating and melting the raw material of the molded article (for example, pellets of the present invention), extruding the molten material from the T-die onto the base material layer, and laminating the polymer layer to the base material layer. In the coextrusion molding process, which is another example of the T-die method, for example, a laminate comprising a polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II) and a base material layer can be produced by extrusion molding while heating and melting both the raw material for the polymer layer and the raw material for the base material layer.

In the extrusion lamination process, in order to obtain good adhesive bonding property with the substrate layer, it is preferable to extrude the raw material of the molded body from a die at a temperature of 140 to 260 ℃.

Examples of the substrate layer include films and sheets of synthetic polymer compounds, metal foils, paper, cellophane, nonwoven fabrics, and woven fabrics. Examples of the synthetic polymer compound include, but are not limited to, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polyamide, polyvinyl alcohol, polycarbonate, cycloolefin resin, styrene-methyl methacrylate copolymer, polyvinyl chloride, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyethylene, polypropylene, and a mixture of 2 or more of these polymers. The synthetic polymer compound may be a copolymer obtained by copolymerizing various monomers. These films and sheets may be further subjected to aluminum deposition, aluminum oxide deposition, or silicon dioxide deposition. Further, these films and sheets of synthetic polymer compounds may be further printed with urethane-based inks and the like.

Examples of the metal foil include aluminum foil, copper foil, and the like, and examples of the paper include kraft paper, high-quality paper, translucent paper, and the like. Examples of the nonwoven fabric include nonwoven fabrics formed of aramid fibers, glass fibers, cellulose fibers, nylon fibers, vinylon fibers, polyester fibers, polyolefin fibers, rayon fibers, and the like. Examples of the woven fabric include woven fabrics formed of aramid fibers, glass fibers, cellulose fibers, nylon fibers, vinylon fibers, polyester fibers, polyolefin fibers, rayon fibers, and the like.

Examples of the structure of the laminate include: a polymer layer comprising an acrylic block copolymer (I) and an acrylic polymer (II) and a 2-layer composition of the base layer, a 2-layer composition of the base layer and a 3-layer composition of a polymer layer comprising an acrylic block copolymer (I) and an acrylic polymer (II) (base layer/polymer layer/base layer), a 2-layer composition of the base layer and a polymer layer comprising an acrylic block copolymer (I) and an acrylic polymer (II) (base layer/polymer layer/base layer), a composition of the base layer and a 2-layer polymer layer (a) and a polymer layer (b) different from the base layer (base layer) and the acrylic polymer (II) (base layer/polymer layer (a)/polymer layer (b)/base layer), a composition of the base layer and a polymer layer (c) comprising an acrylic block copolymer (I) and an acrylic polymer (II) and a polymer layer (a) formed of a material other than the pellets of the present invention and a 4-layer composition of the base layer Substrate layer), a substrate layer 3 layer, and a 5-layer structure of a polymer layer 2 layer containing the acrylic block copolymer (I) and the acrylic polymer (II) (substrate layer/polymer layer/substrate layer), and the like, but are not limited thereto.

The ratio of the thicknesses of the base layer of the laminate and the polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II) is not particularly limited, and the base layer/polymer layer is preferably in the range of 1/1000 to 1000/1, and more preferably in the range of 1/200 to 200/1, from the viewpoint of durability and handling properties of the resulting laminate.

The bonding surface of the base material layer in contact with the polymer layer comprising the acrylic block copolymer (I) and the acrylic polymer (II) may be oxidized by air or ozone gas. In order to improve the adhesiveness to the polymer layer, the adhesive surface of the base material layer may be subjected to known surface treatment such as anchor coating agent treatment, corona discharge treatment, flame treatment, or plasma treatment. In addition, an anchor layer may be formed on a surface of at least one of the polymer layer and the base material layer using an adhesive resin or the like.

Examples of the resin used in the anchor layer include an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, an ionomer, a block copolymer (for example, a styrene-based triblock copolymer such as SIS or SBS, a diblock copolymer, or the like), an ethylene-acrylic acid copolymer, and an ethylene-methacrylic acid copolymer. The anchor layer may be 1 layer or 2 or more layers.

The method of forming the anchor layer is not particularly limited, and for example, the following methods can be mentioned: a method of forming an anchor layer by applying a solution containing the resin to a base material layer; a method of forming an anchor layer on the surface of a base material layer by heating and melting a composition containing the resin or the like to be the anchor layer, using a T die or the like; and the like.

The coextrusion molding method, which is an example of the T-die method, may be any of a feedblock method and a manifold method, and thus may be multilayered, and a laminate of 2 types of 2 layers formed by a base layer and a polymer layer containing an acrylic block copolymer (I) and an acrylic polymer (II), a laminate of 3 types of 3 layers having an intermediate layer between the base layer and the polymer layer, and the like may be produced.

Examples of the material to be used as the base layer in the coextrusion molding process include various synthetic polymer compounds, and examples of suitable synthetic polymer compounds include polyolefins and the like.

Examples of the polyolefin-based material include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene- α -olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, and polypropylene (homopolymer, random copolymer, block copolymer). These polyolefin-based materials may be used alone or as a mixture/composition in any combination. The polypropylene of the block copolymer is particularly preferred as the material of the substrate layer.

Further, the substrate layer may contain additives such as a pigment, an antioxidant, a stabilizer, and an ultraviolet absorber, if necessary. In the laminate, the base material layer is not limited to a single layer, and a plurality of base material layers may be provided. The total thickness of the substrate layer including a single layer or a plurality of layers is preferably 20 μm or more and 100 μm or less, for example.

In addition, the laminate may have an intermediate layer. Examples of the resin that can be used as the intermediate layer include an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, an ionomer, a block copolymer (for example, a styrene-based triblock copolymer such as SIS or SBS, a diblock copolymer, and the like), an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and the like. The intermediate layer may be 1 layer or 2 or more layers, and may be formed by coextrusion molding simultaneously with the base layer and the polymer layer containing the acrylic block copolymer (I) and the acrylic polymer (II).

When the molded article of the present invention is a multilayer article such as a mold or a sheet, a multilayer article having a polymer layer (Z) comprising an acrylic block copolymer (I) and an acrylic polymer (II) and a polymer layer (Y) formed of a material other than the pellet of the present invention can be produced by injection molding a raw material of the molded article (for example, the pellet of the present invention). Examples of the injection molding method include two-color molding and insert molding.

Examples of the polymer constituting the polymer layer (Y) (hereinafter also referred to as layer (Y)) formed of a material other than the pellets of the present invention include acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers; olefin resins such as polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; an ethylene-based ionomer; styrene resins such AS polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, and the like; styrene-methyl methacrylate copolymer; polyester resins such as polyethylene terephthalate, amorphous polyethylene terephthalate (PET-G), polybutylene terephthalate, and polylactic acid; polyamides such as nylon 6, nylon 66, and polyamide elastomers; a polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymers; a polyacetal; polyvinylidene fluoride; a polyurethane; modified polyphenylene ether; polyphenylene sulfide; a silicone rubber modified resin; an acrylic rubber; a silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin rubbers such as IR, EPR and EPDM. The multilayer body may have other layers in addition to the polymer layer (Z) (hereinafter, also referred to as layer (Z)) and the layer (Y) containing the acrylic block copolymer (I) and the acrylic polymer (II).

Examples of the layer (Y) include a layer (YI) containing a polar resin. Examples of the polar resin include acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers; styrene resins such AS polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, and the like; styrene-methyl methacrylate copolymer; polyester resins such as polyethylene terephthalate, amorphous polyethylene terephthalate (PET-G), polybutylene terephthalate, and polylactic acid; polyamides such as nylon 6, nylon 66, and polyamide elastomers; a polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymers; a polyacetal; polyvinylidene fluoride; a polyurethane; modified polyphenylene ether; polyphenylene sulfide; a silicone rubber modified resin; an acrylic rubber; silicone rubber, and the like.

In the multilayer body, the layer (Z) and the layer (YI) are preferably adjacent to each other. The multilayer body has a layer (Z) having low viscosity and excellent transparency, flexibility and impact absorption. Even when a polar resin having high rigidity is used for the layer (YI) containing a polar resin, the layer (YI) can have both excellent properties of flexibility and impact absorbability.

The thickness of the layer (Z) and the layer (Y) constituting the multilayer body is not particularly limited, and from the viewpoint of excellent flexibility and impact absorption of the molded body, the thickness of the layer (Z) is preferably 0.1 to 10mm, more preferably 0.3 to 5mm, further preferably 0.5 to 3mm, and may be 0.7 to 2mm, further may be 1 to 1.5 mm. The thickness of the layer (Y) is preferably 0.3 to 10mm, more preferably 0.5 to 5mm, and still more preferably 1 to 3 mm.

Specific examples of the method for producing the multilayer body include the following methods: a method (method 1) in which the layer (Z) and the layer (Y) are previously formed separately and laminated; a method (method 2) in which the pellets of the present invention in a molten state are arranged on a layer (Y) produced in advance to form a layer (Z); and a method (method 3) in which a polymer in a molten state is arranged on a layer (Z) produced in advance to form a layer (Y). Among them, methods 2 and 3 are preferable in terms of improvement of adhesion between the layer (Z) and the layer (Y), and method 2 is more preferable in terms of easy obtainment of the objective molded article. Further, since the pellet of the present invention has excellent melt flowability, it is preferably formed into the layer (Z) by injection molding, and particularly, it is more preferably insert molding in which the pellet of the present invention in a molten state is injected after disposing the layer (Y) molded in advance in a mold.

The molded article of the present invention can be used in various applications such as optical fields, food fields, medical fields, consumer electronics fields, automobile fields, electric/electronic fields, and building fields, because the molded article has excellent heat resistance, transparency, and flexibility and also has excellent appearance.

Examples of the shape of the molded article include various shapes such as pellets, sheets, plates, pipes, belts, hoses, rods, and granules.

In the automotive field, for example, as automotive interior and exterior members, automotive acoustic panels, instrument panels, airbag covers, bumper members, body panels, weather strips, gaskets, glass run channels, rack & pinion boots, suspension boots, constant velocity joint boots, side trims, moisture-proof mats, signs, leather goods, floor mats, armrests, steering wheel coatings, outer straps, flasher sockets, gears, grips, and the like are used, and flexibility or transparency is exhibited, and functions, concepts, and designs that have not been available so far can be imparted.

In the electric and electronic fields, the housing for electronic devices is excellent in heat resistance, and therefore, for example, the deformation of a smartphone housing accompanied by heat generation of a smartphone terminal or the like can be suppressed, and the housing is excellent in transparency and flexibility, and therefore, design and design properties can be provided, and the housing can be easily detached.

As other applications, the composition can be suitably used for various housings, various terminal plates, printed wiring boards, speakers, microscopes, binoculars, cameras, clocks, VTRs, viewfinders for projection TVs, filters, prisms, Fresnel lenses, substrate protective films for various optical disks (VD, CD, DVD, MD, LD, etc.), photoswitches, optical connectors, liquid crystal displays, light guide films/sheets for liquid crystal displays, flat panel displays, light guide films/sheets for flat panel displays, plasma displays, light guide films/sheets for plasma displays, retardation films/sheets, polarizing plate protective films/sheets, wave plates, light diffusion films/sheets, prism films/sheets, reflection preventing films/sheets, viewing angle expanding films/sheets, anti-glare films/sheets, brightness improving films/sheets, Liquid crystal, display device substrates for electroluminescence, touch panels, light guide films/sheets for touch panels, spacers between various front panels and various modules, and the like.

Further, the present invention can be applied to various liquid crystal display elements such as a mobile phone, a digital information terminal, a pager, a navigation device, a liquid crystal display for a vehicle, a liquid crystal monitor, a light control panel, a display for OA equipment, a display for AV equipment, an electroluminescence display element, a touch panel, and the like.

Further, from the viewpoint of excellent heat resistance, flexibility, and the like, for example, the present invention can be suitably used as interior/exterior members for buildings, such as curtain walls, roof members, roof materials, window members, rain gutters, exterior materials, wall materials, flooring materials, building materials, coated steel sheets, coated plywood, weather strips for doors or window frames, and the like.

Further, the film can be used for road construction members, retroreflective films/sheets, light-shielding films/sheets, heat-insulating films/sheets, agricultural films/sheets, lighting housings, signboards, translucent sound-shielding walls, and the like.

Further, the rubber composition can be effectively used for various vibration-proof rubbers, vibration-damping members such as vibration-proof rubbers, gaskets, sheets, cushion pads, shock absorbers, pads, rubber mounts, and the like; materials for footwear such as sports shoes, fashion sandals, and the like; components for household appliances such as televisions, stereos, dust collectors, refrigerators, and the like; grips for scissors, drivers, toothbrushes, pens, cameras, ski poles, etc.; office components such as copier conveyance rollers, take-up rollers, and the like; furniture such as sofas, chair tops, etc.; switch shell, truckle, plug, foot glue, earphone; sporting goods such as underwater glasses, breathing tubes, ski boots, ski shoes, skis, ski covers, and golf ball cases; industrial materials such as conveyor belts, electric belts, granulation rollers, and the like; a telescopic member made of sanitary materials such as paper diapers, cataplasm materials, binding bands and the like; hair band, wrist band, watch band, glasses band, etc.; food packaging materials such as wrap films; medical devices such as infusion bags, syringes, catheters, rolling catheters, and the like; stoppers for containers for storing foods, beverages, medicines, and the like; anti-skid chains, wire coatings, trays, films, sheets, stationery, toys, daily sundries and the like.

The laminate of 1 type of the molded article of the present invention can be used for various applications. Examples thereof include adhesive tapes and adhesive films for surface protection, masking, packaging/sealing, office work, labeling, decoration/display, book production, dicing tapes, medical/sanitary use, laminated glass use, glass scattering prevention use, electrical insulation use, electronic device holding and fixing use, semiconductor production use, optical display films use, adhesive optical films use, electromagnetic wave shielding use, and sealing materials for electric/electronic components. Specific examples are given below.

The surface protection material can be used for various materials such as metal, plastic, rubber, and wood, and specifically, can be used for surface protection of coated surfaces, plastic working of metal, deep drawing, automobile members, and optical members. Examples of the automotive member include a painted outer panel, a wheel, a mirror, a window, a lamp cover, and the like. As the optical member, various image display devices such as a liquid crystal display, an organic EL display, a plasma display, and a field emission display; polarizing film, polarizing plate, phase difference plate, light guide plate, diffusion plate, DVD, etc.; for precision fine coated panels for electronic/optical applications, and the like.

Examples of the masking use include masking in the production of printed wiring boards and flexible printed wiring boards; plating in electronic equipment, masking at the time of solder treatment; the production of vehicles such as automobiles, the coating of vehicles and buildings, textile printing, and masking at the end of civil engineering works.

Examples of the packaging applications include weight packaging, output packaging, sealing of corrugated cardboard boxes, and can sealing. Examples of office applications include general office use, sealing, book repair, drawing, and memo recording. Examples of the label application include price, merchandise display, label, POP, sticker, tape, nameplate, decoration, advertisement, and masking film.

Examples of the label application include papers such as paper, processed paper (paper subjected to aluminum deposition processing, aluminum lamination processing, lacquer processing, resin processing, and the like), synthetic paper, and the like; labels having a base material layer such as cellophane, plastic material, cloth, wood or metal film. Examples of the substrate layer include high-quality paper, coated paper, glossy paper, hot paper, foil paper, polyethylene terephthalate film, polyvinyl chloride film, OPP film, polylactic acid film, synthetic paper, synthetic hot paper, and outer laminate film.

Examples of the adherend of the label include plastic products such as plastic bottles and foamed plastic cases; paper/corrugated paper products such as corrugated boxes; glass products such as glass bottles; a metal article; other inorganic materials such as ceramics.

Examples of the decoration and display applications include a hazard label sticker, a thread tape, a wiring mark, a phosphor tape, a reflective sheet, and the like.

Examples of the application of the pressure-sensitive adhesive optical film include optical films in which a pressure-sensitive adhesive layer is formed on at least a part or all of one or both surfaces of a polarizing film, a polarizing plate, a retardation film, a viewing angle expanding film, a brightness improving film, an antireflection film, an antiglare film, a color filter, a light guide plate, a diffusion film, a prism sheet, an electromagnetic wave shielding film, a near infrared ray absorbing film, a functional composite optical film, an ITO-laminating film, an impact resistance-imparting film, a visibility-improving film, and the like. The pressure-sensitive adhesive optical film also includes a protective film for protecting the surface of the optical film. The pressure-sensitive adhesive optical film is suitably used for various image display devices such as liquid crystal display devices, PDPs, organic EL display devices, electronic papers, game machines, and mobile terminals.

Examples of the electrical insulation application include protective coating and insulation of a coil, and interlayer insulation of a motor and a transformer. Examples of the use for holding and fixing electronic devices include carrier tapes, packaging, fixing and splicing braun tubes, reinforcing ribs, and the like. Examples of the semiconductor manufacturing include protection of a silicon organic wafer.

Examples of medical/sanitary uses include transdermal drug uses such as analgesic and anti-inflammatory agents (plaster and cataplasm), cold patches, itching relieving patches, and keratolytic agents; various belt uses such as first aid adhesive plaster (added with bactericide), operation dressing/operation belt, adhesive plaster, tourniquet, belt for human excrement treatment wearing device (artificial anus fixing belt), belt for suture, antibacterial belt, fixing patch, self-adhesive bandage, oral mucosa adhesive belt, belt for sport, and belt for alopecia; cosmetic applications such as facial masks, eye moisturizing sheets, exfoliating dressings, and the like; use in combination with sanitary materials such as diapers and pet sheets; cooling fins, warm-up, dust-proof, waterproof, pest-catching, etc.

Examples of applications of the sealing material for electronic/electrical components include liquid crystal displays, organic EL illuminators, solar cells, and the like.

As the application of the laminated glass, it can be effectively used for automobile windshields, automobile side window glasses, automobile skylights, automobile rear glass, head-up display glasses, and the like.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties in the examples and comparative examples were measured or evaluated by the following methods.

"weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn)"

The weight average molecular weight and the number average molecular weight of the acrylic block copolymer were determined by gel permeation chromatography (hereinafter abbreviated as GPC) based on polystyrene equivalent molecular weights, and the molecular weight distribution was calculated from these values. The details of the conditions for measuring the molecular weight are as follows.

An apparatus: GPC apparatus "HLC-8020" manufactured by Tosoh corporation "

Separation column: "TSKgel GMHXL", "G4000 HXL" and "G5000 HXL", manufactured by Tosoh corporation, were connected in series "

Eluent: tetrahydrofuran (THF)

Eluent flow rate: 1.0 ml/min

Column temperature: 40 deg.C

The detection method: differential Refractive Index (RI)

"composition ratio of respective Polymer segments"

By passing¹H-NMR measurement was conducted.

An apparatus: JNM-LA400 nuclear magnetic resonance device manufactured by Nippon electronic Co., Ltd "

Deuterated solvents: deuterated chloroform

¹In the H-NMR spectrum, signals in the vicinity of 3.6ppm, 3.7ppm and 4.0ppm were respectively assigned to a hydrogen atom (-O-C) bonded to a carbon atom adjacent to the oxygen atom contained in the ester group of the methyl methacrylate unit ₃H) And a hydrogen atom (-O-C) bonded to a carbon atom adjacent to the oxygen atom contained in the ester group of the methyl acrylate unit ₃H) And a hydrogen atom (-O-C) bonded to a carbon atom adjacent to the oxygen atom contained in the ester group of the n-butyl acrylate unit ₂H-CH₂-CH₂-CH₃) The molar ratio of each monomer unit is determined from the ratio of the integrated values thereof, and the content of each polymer segment is determined by converting the molar ratio into a mass ratio based on the molecular weight of the monomer unit.

Melt flow Rate "

The Melt Flow Rate (MFR) of the polymers obtained in examples and comparative examples was measured in accordance with ISO 1133 at 230 ℃ under a load of 3.8kg for 10 minutes.

Evaluation of pellet blocking resistance "

The pellets obtained in examples and comparative examples were transferred to a 100ml beaker made of plastic, and a weight was placed thereon so that the load per unit area became 103g/cm²Putting into a dryer at 40 deg.C for 1 week,the sticking state of the pellets when they were taken out from the plastic beaker was visually observed.

AA: complete disintegration of the granules

A: some of the pellets were in the form of a lump, but were easily disintegrated by touching with a finger

B: part of the pellet is in block form, and is not easily disintegrated even by touching with finger

Evaluation of transparency of pellets "

The pellets obtained in examples and comparative examples were visually observed.

a: has no turbid white feeling and high transparency

b: slight feeling of white turbidity

"evaluation of compatibility Using pressurized sheet"

The pressure sheet produced in the reference example was visually observed.

1: no turbid white feeling, high transparency, and high compatibility

2: slightly cloudy, but slightly more compatible.

3: strong white turbidity feeling and poor compatibility.

Production example 1 [ production of acrylic triblock copolymer (I-1) ]

(1) A three-way valve was placed in a 2L three-necked flask, the interior was replaced with nitrogen, and while stirring at room temperature, toluene 938g and 1, 2-dimethoxyethane 20.2g were added, followed by addition of a toluene solution containing 20.8mmol of isobutylbis (2, 6-di-tert-butyl-4-methylphenoxy) aluminum 41.4g and further addition of a cyclohexane solution containing 2.60mmol of sec-butyllithium 1.53 g.

(2) Then, 21.8g of methyl methacrylate was added thereto at room temperature with stirring, and further stirring was continued for 60 minutes. The reaction solution was initially colored yellow, but was colorless after stirring for 60 minutes.

(3) Thereafter, the internal temperature of the polymerization solution was cooled to-30 ℃ and 246g of a mixed solution of methyl acrylate and n-butyl acrylate (mass ratio 50/50) was added dropwise over 2 hours under stirring, and stirring was continued at-30 ℃ for a further 5 minutes after the completion of the addition.

(4) Thereafter, 25.2g of methyl methacrylate was added thereto, and the mixture was stirred at room temperature overnight.

(5) After the polymerization reaction was stopped by adding 12.2g of methanol, the resulting reaction solution was poured into 15kg of methanol under stirring to precipitate a white precipitate. The resulting white precipitate was recovered and dried to obtain 260g of an acrylic triblock copolymer (I-1). The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained acrylic triblock copolymer (I-1) were determined by GPC measurement by the above-mentioned method, and the molecular weight distribution (Mw/Mn) was calculated. In addition, by the above¹H-NMR measurement was carried out to determine the total content of the polymer segments containing methyl methacrylate units in the acrylic triblock copolymer (I-1). The properties of the acrylic triblock copolymer (I-1) are shown in Table 1.

Production example 2 [ production of acrylic triblock copolymer (I-2) ]

(1) A three-way valve was placed in a 2L three-necked flask, the interior was replaced with nitrogen, and while stirring at room temperature, toluene 938g and 1, 2-dimethoxyethane 20.2g were added, followed by addition of a toluene solution containing 20.8mmol of isobutylbis (2, 6-di-tert-butyl-4-methylphenoxy) aluminum 41.4g and further addition of a cyclohexane solution containing 2.60mmol of sec-butyllithium 1.53 g. (2) Then, 21.8g of methyl methacrylate was added thereto at room temperature with stirring, and further stirring was continued for 60 minutes. The reaction solution was initially colored yellow, but was colorless after stirring for 60 minutes.

(3) Thereafter, the internal temperature of the polymerization solution was cooled to-30 ℃ and 246g of a mixed solution of methyl acrylate and n-butyl acrylate (mass ratio 75/25) was added dropwise over 2 hours under stirring, and stirring was continued at-30 ℃ for a further 5 minutes after the completion of the addition.

(4) Thereafter, 25.2g of methyl methacrylate was added thereto, and the mixture was stirred at room temperature overnight.

(5) After the polymerization reaction was stopped by adding 12.2g of methanol, the resulting reaction solution was poured into 15kg of methanol under stirring to precipitate a white precipitate. The resulting white precipitate was recovered and dried to obtain 260g of an acrylic triblock copolymer (I-2). Obtained by GPC measurement by the above-mentioned methodThe weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic triblock copolymer (I-2) were determined to calculate the molecular weight distribution (Mw/Mn). In addition, by the above¹H-NMR measurement was carried out to determine the total content of the polymer segments containing methyl methacrylate units in the acrylic triblock copolymer (I-2). The properties of the acrylic triblock copolymer (I-2) are shown in Table 1.

Production example 3 [ production of acrylic triblock copolymer (II-1A-1 ]

(1) A three-way valve was placed in a 2L three-necked flask, the interior was replaced with nitrogen, and while stirring at room temperature, 936g of toluene and 51.4g of 1, 2-dimethoxyethane were added, 32.9g of a toluene solution containing 16.5mmol of isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) aluminum and 4.10g of a cyclohexane solution containing 7.00mmol of sec-butyllithium were further added.

(2) Subsequently, 65.0g of methyl methacrylate was added thereto at room temperature with stirring, and stirring was continued for further 60 minutes. The reaction solution was initially colored yellow, but was colorless after stirring for 60 minutes.

(3) Then, the internal temperature of the polymerization solution was cooled to-30 ℃ and 226g of n-butyl acrylate was added dropwise over 2 hours under stirring, and stirring was continued at-30 ℃ for a further 5 minutes after the completion of the addition.

(4) Thereafter, 161g of methyl methacrylate was added thereto, and the mixture was stirred at room temperature overnight.

(5) After 13.7g of methanol was added to stop the polymerization reaction, the obtained reaction solution was poured into 15kg of methanol under stirring to precipitate a white precipitate. The resulting white precipitate was recovered and dried to obtain 430g of an acrylic triblock copolymer (II-1A-1). The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained acrylic triblock copolymer (II-1A-1) were determined by GPC measurement by the above-mentioned method, and the molecular weight distribution (Mw/Mn) was calculated. In addition, by the above¹H-NMR measurement was carried out to determine the total content of the polymer segments containing methyl methacrylate units in the acrylic triblock copolymer (II-1A-1). The properties of the acrylic triblock copolymer (II-1A-1) are shown in Table 2.

Production example 4 [ production of acrylic triblock copolymer (II-1A-2 ]

(1) A three-way valve was placed in a 2L three-necked flask, and after the inside was replaced with nitrogen, 1029g of toluene and 51.4g of 1, 2-dimethoxyethane were added thereto while stirring at room temperature, 32.9g of a toluene solution containing 16.5mmol of isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) aluminum and 4.51g of a cyclohexane solution containing 7.70mmol of sec-butyllithium were further added thereto.

(2) Subsequently, 50.0g of methyl methacrylate was added thereto at room temperature with stirring, and stirring was continued for further 60 minutes. The reaction solution was initially colored yellow, but was colorless after stirring for 60 minutes.

(3) Thereafter, the internal temperature of the polymerization solution was cooled to-30 ℃ and 209g of n-butyl acrylate was added dropwise over 2 hours under stirring, and stirring was continued at-30 ℃ for a further 5 minutes after the completion of the addition.

(4) Thereafter, 82.0g of methyl methacrylate was added thereto, and the mixture was stirred at room temperature overnight.

(5) After 13.7g of methanol was added to stop the polymerization reaction, the obtained reaction solution was poured into 15kg of methanol under stirring to precipitate a white precipitate. The resulting white precipitate was recovered and dried to obtain 330g of an acrylic triblock copolymer (II-1A-2). The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained acrylic triblock copolymer (II-1A-2) were determined by GPC measurement by the above-mentioned method, and the molecular weight distribution (Mw/Mn) was calculated. In addition, by the above¹H-NMR measurement was carried out to determine the total content of the polymer segments containing methyl methacrylate units in the acrylic triblock copolymer (II-1A-2). The properties of the acrylic triblock copolymer (II-1A-2) are shown in Table 2.

Production example 5 [ production of acrylic triblock copolymer (III-1) ]

(1) A three-way valve was placed in a 2L three-necked flask, the interior was replaced with nitrogen, and while stirring at room temperature, 936g of toluene and 51.4g of 1, 2-dimethoxyethane were added, 32.9g of a toluene solution containing 16.5mmol of isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) aluminum and 3.88g of a cyclohexane solution containing 6.62mmol of sec-butyllithium were further added.

(2) Subsequently, 52.9g of methyl methacrylate was added thereto at room temperature with stirring, and stirring was continued for further 60 minutes. The reaction solution was initially colored yellow, but was colorless after stirring for 60 minutes.

(3) Then, the internal temperature of the polymerization solution was cooled to-30 ℃ and 226g of n-butyl acrylate was added dropwise over 2 hours under stirring, and stirring was continued at-30 ℃ for a further 5 minutes after the completion of the addition.

(4) Thereafter, 46.2g of methyl methacrylate was added thereto, and the mixture was stirred at room temperature overnight.

(5) After 13.7g of methanol was added to stop the polymerization reaction, the obtained reaction solution was poured into 15kg of methanol under stirring to precipitate a white precipitate. The resulting white precipitate was recovered and dried to obtain 300g of an acrylic triblock copolymer (III-1). The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained acrylic triblock copolymer (III-1) were determined by GPC measurement by the above-mentioned method, and the molecular weight distribution (Mw/Mn) was calculated. In addition, by the above¹H-NMR measurement was carried out to determine the total content of the polymer segments containing methyl methacrylate units in the acrylic triblock copolymer (III-1). The properties of the acrylic triblock copolymer (III-1) are shown in Table 2.

Production example 6 [ production of acrylic resin Fine particles ]

Acrylic resin (methyl methacrylate unit content: 90 mass%, weight average molecular weight: 85000) was subjected to primary pulverization using an impact Pulverizer (homokawa Micron co., ltd., ACM Pulverizer-10) and secondary pulverization using a Counter jet mill (homokawa Micron co., ltd., 200AFG), thereby producing acrylic resin fine particles having a particle size distribution D50 value of 6 μm.

The block structures, weight average molecular weights (Mw), molecular weight distributions (Mw/Mn), total contents of PMMA polymer segments (polymer segments containing 100 mass% of methyl methacrylate units) constituting the polymer segment (a1), constituent components of the polymer segment (B1), and mass ratios in the polymer segment (B) of the acrylic triblock copolymers (I-1) to (I-2) obtained in production examples 1 to 2 are shown in table 1. In Table 1, PMMA means a polymer segment containing 100 mass% of methyl methacrylate units, and PMA/PnBA means a segment composed only of methyl acrylate units and n-butyl acrylate units.

The block structures, weight average molecular weights (Mw), molecular weight distributions (Mw/Mn), total methyl methacrylate unit contents, MFR at 230 ℃ under a load of 3.8kg of the acrylic triblock copolymers (II-1A-1) to (II-1A-2) and (III-1) obtained in production examples 3 to 5 are shown in Table 2. In table 2, PMMA means a polymer segment containing 100 mass% of methyl methacrylate units, and PnBA means a segment containing 100 mass% of n-butyl acrylate units.

[ Table 1]

[ Table 2]

Examples 1,2, 6 to 12

A mixture of the obtained acrylic triblock copolymer (I-1) or (I-2) and the acrylic triblock copolymer (II-1A-1) or (II-1A-2) was prepared by dry-blending in advance at the ratio shown in Table 3, and the mixture was melt-kneaded in a twin-screw extruder ("JSW-JBaII" manufactured by Nippon Steel Co., Ltd.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by an underwater cutting method to obtain pellets (A' -1,2, 6 to 12). Thereafter, Aerosil R972 was pulverized so that the concentration thereof with respect to the mass of the pellets (A' -1,2, 6 to 12) became the concentration shown in Table 3, thereby obtaining pellets (A-1, 2,6 to 12). The obtained pellet had good transparency and was "a". Further, the blocking resistance was "a" or "AA", which was not easily blocked and was good, and the obtained pellets were found to have excellent handling properties. The results are shown in Table 3.

EXAMPLES 3 to 5

A mixture of the obtained acrylic triblock copolymer (I-1) and the acrylic triblock copolymer (II-1A-1) dry-blended in advance at the ratio shown in Table 3 was prepared, and the mixture was melt-kneaded in a twin-screw extruder ("ZSK-25" manufactured by KRUPP WERNER & PFLEIDER Co.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by a strand cutting method to obtain pellets (A' -3-5). Thereafter, Aerosil R972 was pulverized so that the concentration thereof with respect to the mass of the pellets (A' -3 to 5) became the concentration shown in Table 3, thereby obtaining pellets (A-3 to 5). The obtained pellet had good transparency and was "a". Further, the "AA" for the blocking resistance was found to be not easily blocked and was found to be good, and the obtained pellets were found to be excellent in handling property. The results are shown in Table 3.

EXAMPLES 13 to 15

An acrylic triblock copolymer (I-1) obtained by dry blending in advance at a ratio shown in table 3 was prepared as a mixture with an acrylic random copolymer (II-2A-1) (Kuraray co., ltd., "paranet (registered trademark) GF") having an MFR of 15g/10 minutes under conditions of a temperature of 230 ℃ and a load of 3.8kg and a content of methyl methacrylate units of 80 mass% or more, and the mixture was melt-kneaded in a twin-screw extruder ("JSW-JBaII" manufactured by japan steel corporation). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by underwater cutting to obtain pellets (A' -13 to 15). Thereafter, Aerosil R972 was pulverized so that the concentration thereof with respect to the mass of the pellets (A' -13 to 15) became the concentration shown in Table 3, thereby obtaining pellets (A-13 to 15). The obtained pellet had transparency "b" and a slightly cloudy feeling, but was "a" or "AA" for blocking resistance, and was not easily blocked, and was good, and the obtained pellet was found to have excellent handling properties. The results are shown in Table 3.

EXAMPLE 16

Pellets (a-27) were obtained by crushing the fine acrylic resin particles obtained in production example 6 in the same manner as in example 12 except that the anti-blocking agent was changed from Aerosil R972 to fine acrylic resin particles obtained in production example 6. The obtained pellet had good transparency and was "a". Further, the "AA" for the blocking resistance was found to be not easily blocked and was found to be good, and the obtained pellets were found to be excellent in handling property. The results are shown in Table 3.

Comparative examples 1,3,5 to 7

The obtained acrylic triblock copolymer (I-1) or (I-2) was melt-kneaded in a twin-screw extruder ("ZSK-25" manufactured by KRUPP WERNER & PFLEIDERER Co.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by a strand cutting method to obtain pellets (A' -16, 18, 20 to 22). Then, the anti-blocking agents shown in Table 3 were crushed to a predetermined concentration to obtain (A-16, 18, 20 to 22). The obtained pellet had transparency "b" and a slight white turbidity feeling due to a large amount of the anti-blocking agent added. Further, the blocking resistance was also "B", which was liable to cause blocking, and it was found that the obtained pellets had poor handling properties. The results are shown in Table 3.

Comparative examples 2 and 4

The obtained acrylic triblock copolymer (I-1) was melt-kneaded in a twin-screw extruder ("JSW-JBaII" manufactured by Nippon Steel Co., Ltd.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by an underwater cutting method to obtain pellets (A' -17, 19). Then, the anti-blocking agents shown in Table 3 were crushed to a predetermined concentration to obtain (A-17, 19). The obtained pellet had transparency "b" and a slight white turbidity feeling due to a large amount of the anti-blocking agent added. Further, the blocking resistance was also "B", which was liable to cause blocking, and it was found that the obtained pellets had poor handling properties. The results are shown in Table 3.

Comparative examples 8 to 10

An acrylic triblock copolymer (I-1) obtained by dry blending in advance at a ratio shown in table 3 was prepared as a mixture with an acrylic random copolymer (III-2) (Kuraray co., ltd., "paranet (registered trademark) G") having an MFR of 8.0G/10 minutes under a condition of a temperature of 230 ℃ and a load of 3.8kg and a content of methyl methacrylate units of 80 mass% or more, and the mixture was melt-kneaded in a twin-screw extruder ("JSW-JBaII", manufactured by japan steel manufacturing, ltd.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by underwater cutting to obtain pellets (A' -23 to 25). Thereafter, Aerosil R972 was pulverized so that the concentration thereof with respect to the mass of the pellets (A' -23 to 25) became the concentration shown in Table 3, thereby obtaining pellets (A-23 to 25). The obtained pellet had transparency "b" and a slightly cloudy feeling. Further, the blocking resistance was also "B", which was liable to cause blocking, and it was found that the obtained pellets had poor handling properties. The results are shown in Table 3.

Comparative example 11

A mixture of the obtained acrylic triblock copolymer (I-1) and the acrylic triblock copolymer (III-1) dry-blended in advance at the ratio shown in Table 3 was prepared, and the mixture was melt-kneaded in a twin-screw extruder ("JSW-JBaII" manufactured by Nippon Steel Co., Ltd.). The obtained melt-kneaded product was extruded from a twin-screw extruder and pelletized by an underwater cutting method to obtain pellets (A' -26). Thereafter, Aerosil R972 was broken up so that the mass of Aerosil R972 with respect to the mass of the pellets (A' -26) became the concentration shown in Table 3, thereby obtaining pellets (A-26). The obtained pellet had transparency "b" and a slight white turbidity feeling due to a large amount of the anti-blocking agent added. Further, the blocking resistance was also "B", which was liable to cause blocking, and it was found that the obtained pellets had poor handling properties. The results are shown in Table 3.

[ Table 3]

EXAMPLE 17

The pellets (A-9) obtained in example 9 were charged into a single-screw extruder from a hopper, heated and melted at a temperature of 180 ℃ to form a polymer layer (T die method) of 300mm in width and 100 μm in thickness, which was formed from the pellets (A-9) and laminated on a PET film (250 μm in thickness, "E5001" manufactured by Toyo chemical Co., Ltd.) through a T die disposed at the tip of the single-screw extruder, and the release-treated surface was further covered with silicon release-treated PET (50 μm in thickness, "A31" manufactured by TEIJIN Solutions Co., Ltd.) and brought into contact with the surface of the polymer layer to prepare a laminated film. The take-up rate was set to 2.0 m/min. The pellets (A-9) used had excellent blocking resistance, and therefore, they could be fed to a single-screw extruder at a stable speed without causing blocking, and therefore, the thickness variation was as small as. + -. 5 μm, and a highly precise laminated film could be obtained. The obtained film has high transparency and excellent blocking resistance, and is highly flexible.

EXAMPLE 18

A laminated film was produced in the same manner as in example 17, except that the thickness of the polymer layer formed from the pellets (a-9) was changed to 200 μm. It is possible to obtain a thin film with high accuracy, in which the thickness of the thin film is not all + -5 μm.

EXAMPLE 19

Polycarbonate ("Iipilon S2000" manufactured by Mitsubishi Engineering-Plastics Corporation) was charged into an injection molding machine ("UH 1000-80" manufactured by Nissus resin industries, Ltd.) in which the cylinder temperature was set to 290 ℃ and the mold temperature was set to 90 ℃ to prepare a molded article which was a polymer layer (Y) for insert molding having a length of 100mm × a width of 40mm and a thickness of 1 mm. Then, the obtained molded article of the layer (Y) was mounted in contact with the bottom surface of an injection mold having a length of 100mm × a width of 40mm and a thickness of 2mm, and pellets (A-9) were injected into the gap of the mold by the injection molding machine having a barrel temperature of 180 ℃ and a mold temperature of 50 ℃ to produce a multilayer body having the layer (Z) and the layer (Y) (insert molding). The obtained multilayer body was transparent and had good adhesion between 2 layers.

EXAMPLE 20

A multilayer body was produced by insert molding in the same manner as in example 19, except that the pellet (A-9) was changed to the pellet (A-12). The obtained multilayer body was transparent and had good adhesion between 2 layers.

EXAMPLES 21 to 26

A mixture in which the pellets (A-9) obtained in example 9, an antioxidant, a light stabilizer and an ultraviolet absorber were dry-mixed in advance at the ratio shown in Table 5 was prepared, and the mixture was melt-kneaded in a twin-screw extruder (KRUPP WERER & PFLEIDER "ZSK-25") having a cylinder temperature of 180 ℃. The obtained melt-kneaded product was extruded from a twin-screw extruder, pelletized by a strand cutting system, and further added with 300ppm of Aerosil R972 as an anti-blocking agent to obtain pellets as a raw material of a molded article. Then, a sheet-like molded article having a length of 5cm × a width of 5cm and a thickness of 3mm was produced from the obtained pellets by an injection molding machine ("SE 18 DU" from Sumitomo heavy mechanical industries, Ltd.) in which the cylinder temperature was set to 180 ℃ and the mold temperature was set to 50 ℃. The haze value of the molded article was measured according to ISO 14782 using a direct-reading haze meter (manufactured by Nippon Denshoku industries Co., Ltd.), and the total light transmittance of the molded article was measured according to ISO 13468-1. Further, the color characteristics (b) in the L.a.b.color system were measured using SD5000 (measurement conditions: light source D65, field of view 2 ℃ C.) manufactured by Nippon Denshoku industries Co., Ltd. The appearance of the molded article was as follows: when the whole was visually confirmed, the case where there was no unevenness was judged to be "clear", and the case where there was unevenness was judged to be "unclear".

Then, a QUV weatherometer (manufactured by Q-LAB Co., Ltd.; light source: UV-340, 0.60W/m)²) The obtained sheet-like molded article was subjected to accelerated weathering test (test conditions: the total of UV irradiation (60 ℃ C., 8 hours) and water spraying (50 ℃ C., 4 hours) was set to 12 hours for 1 cycle, and the total was 168 hours for 14 cycles). Further, the sheet-like molded article after accelerated weathering test was also evaluated for haze value, total light transmittance, color characteristics (b), and appearance under the above measurement conditions. The results are shown in Table 4. In table 4, 2 values in each column of the haze value, total light transmittance, and color characteristic (b) are values before the weathering test is promoted on the left side and values after the weathering test is promoted on the right side.

As shown in table 4, it is found that, particularly in the case of adding the antioxidant, the light stabilizer, the ultraviolet absorber and the like in examples 22 to 25, the change in the color characteristics before and after the accelerated test can be further reduced.

The additives (antioxidant, light stabilizer, and ultraviolet absorber) used in the above examples are shown below.

< additive >

Phenolic antioxidant

ADECASTAB AO-60: manufactured by ADEKA, Inc

Pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenoxy) propionate ]

Phosphorus-based antioxidant

ADECASTAB PEP-36: manufactured by ADEKA, Inc

3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane

Light stabilizers

Tinuvin 144: manufactured by BASF corporation

Bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) - [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] butyl malonate

Ultraviolet absorber

Viosorb 583: common drugs manufactured by Kyowa Kagaku K.K.

2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) -2-phenol

ADECASTAB LA-31 RG: manufactured by ADEKA, Inc

2, 2' -methylenebis 6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol ]

ADECASTAB LA-46: manufactured by ADEKA, Inc

(2- (4, 6-Diphenyl-1, 3, 5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy ] phenol

[ Table 4]

The left side of each column of 1 is a value before the weather resistance test is promoted, and the right side is a value after the weather resistance test is promoted.

EXAMPLES 27 to 29

The pellets (A-9) obtained in example 9 and, if necessary, a non-reactive silicone oil were charged into LABO PLASTOMILL at the ratio shown in Table 5, and they were melt-kneaded at a temperature of 180 ℃ and a rotation speed of 50rpm for 5 minutes, and the obtained melt-kneaded product was taken out. From the obtained melt-kneaded product, a sheet-like molded article having a length of 3cm, a width of 6mm and a thickness of 3mm was produced by using a Minimax set at a temperature of 200 ℃. The haze value of the molded article was measured according to ISO 14782 using a direct-reading haze meter (manufactured by Nippon Denshoku industries Co., Ltd.), and the total light transmittance of the molded article was measured according to ISO 13468-1. After one week of the molded article production, the appearance was visually checked to confirm the presence or absence of bleeding of the components contained in the molded article. The lubricity of the surface was judged by the touch of the surface of the obtained molded article with a finger. The results are shown in Table 5.

In example 28 in which a side chain polyether-modified silicone oil (KF351A) which is a non-reactive silicone oil was added as a lubricant, it was confirmed that the lubricity of the surface was higher than that of example 27 in which no lubricant was added, while the transparency was maintained.

Hereinafter, additives (lubricants) used in the above-described examples are shown.

< additive >

Lubricant (non-reactive silicone oil)

KF 351A: modified side chain polyether type product of shin-Etsu chemical Co., Ltd

KF 6002: modified type of hydroxyl group at both ends, manufactured by shin-Etsu chemical Co., Ltd

[ Table 5]

Examples 30 and 31

The pellets (a-9) obtained in example 9 and titanium oxide were charged into LABO plastics at the ratio shown in table 6, and they were melt-kneaded at a temperature of 230 ℃ and a rotation speed of 50rpm for 5 minutes to obtain a raw material for a molded article in which titanium oxide was uniformly dispersed. The raw material of the obtained molded article was heated at 200 ℃ under a pressure of 50kgf/cm²Was press-molded under the conditions described above to prepare a 300 μm thick sheet. The total light transmittance of the sheet was measured by a direct-reading haze meter (manufactured by Nippon Denshoku industries Co., Ltd.) in accordance with ISO 13468-1. According to (light shielding rate) < 1- (total light transmittance)) The light shielding rate was calculated. The results are shown in Table 6.

In these examples, the light shielding rate was 98.5% or more, although the light shielding rate was a thin sheet of 300 μm.

Hereinafter, additives (fillers) used in the above examples are shown.

< additive >

Filler material

Titanium oxide: CR90, product of Shidai industries, Ltd

[ Table 6]

EXAMPLES 32 to 36

The pellet (A-12) obtained in example 12 and another polymer were kneaded with LABO PLASTOMILL in accordance with the kind, mixing ratio and kneading temperature of the other polymer shown in Table 7 below. The resulting mixture was press-molded using a spacer having a thickness of 1mm at a temperature shown in Table 7. The compatibility of the resulting pressure sheet was evaluated by visual observation, and as a result, examples 33 to 35 had a high compatibility of "1". In examples 32 and 36, although slightly cloudy, the compatibility was "2" which is slightly high, and the compatibility with other polymers used in examples 32 to 36 was slightly high. The results are shown in Table 7.

< other Polymer >

Polycarbonate: ifpilon S-3000, manufactured by Mitsubishi Engineering-Plastics Corporation

Acrylic resin: kuraray co, ltd, paranet (registered trademark) GF

Styrene-based thermoplastic elastomer: kuraray co., ltd, SEPTON (registered trademark) 2004

Styrene-based thermoplastic elastomer: kuraray co., ltd. system, HYBRAR (registered trademark) 7311

PET-G: eastar GN007 manufactured by Eastman corporation

From the above, it is understood that the pellets comprising the acrylic triblock copolymer (I) of the present invention and the acrylic polymer (II) are excellent in anti-blocking property and contribute to the handling of the pellets.

[ Table 7]